CN108777296A - A kind of surface is modified nickelic tertiary cathode material and its prepares and its manufactured battery - Google Patents
A kind of surface is modified nickelic tertiary cathode material and its prepares and its manufactured battery Download PDFInfo
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- CN108777296A CN108777296A CN201810563895.8A CN201810563895A CN108777296A CN 108777296 A CN108777296 A CN 108777296A CN 201810563895 A CN201810563895 A CN 201810563895A CN 108777296 A CN108777296 A CN 108777296A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01—ELECTRIC ELEMENTS
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The present invention provides a kind of surface modification nickelic tertiary cathode material, is the clad surface modified layer on nickelic tertiary cathode material kernel；The nickelic tertiary cathode material kernel is Li1+ kNixCoyMzO2, -0.1≤k≤0.1,0 < x <, 1,0 < y <, 1,0 < z < 1.Surface reforming layer is by two kinds of surface modifying species at one of which is yttria-stabilized zirconia, another is selected from metal oxide MeOx, metal fluoride MeFx, metal phosphate Me (PO4)xOr at least one of C.The present invention also provides the surfaces to be modified the preparation method of nickelic tertiary cathode material and the battery being made from it.Surface provided by the invention is modified nickelic tertiary cathode material, and surface modifying species are coated on bulk material surface, reduce the side reaction of nickelic tertiary cathode material and electrolyte, it is suppressed that the irreversible capacity loss of material improves cycle performance.
Description
Technical field
The invention belongs to battery material fields, and in particular to a kind of tertiary cathode material of lithium ion battery, its preparation side
Battery made of method, the positive electrode.
Background technology
It is firstly introduced stratiform oxo transition metal since Sony designed the first generation lithium ion battery produced in 1991
Compound cobalt acid lithium (LiCoO2) it is used as positive electrode, from initial small portable electronic device electric vehicle finally and storage
Energy power grid, the application of lithium ion battery are gradually extensive.
When relative to lithium anode blanking voltage 4.2V, cobalt acid lithium (LiCoO2) anode actual specific capacity be
140mAh g-1, disclosure satisfy that the primary demand of portable electronic device.Further, close to high-energy for continuous improvement
Degree, the demand of low cost and environmental suitability, the Li [Ni formed by the parts Co and Al doped and substituted NixCoyAlz]O2It is nickelic
Ternary material (NCA), due to its height ratio capacity, high-energy density and low cost and receive much attention, it is considered to be high-energy at present
One of optimal candidate positive electrode of density lithium ion battery.However, the system material is as high energy lithium ion cell candidate
Material there is also some problems：First, due to Ni during high―temperature nuclei3+It is unstable, be easy to be reduced into Ni2+And by
InWithClose ionic radius and resulting Li+/Ni2+Mixing leads to lithium ion
Solid-state diffusion it is more difficult, increase the polarization of material；Secondly as the Ni easily restored4+Chemical instability, especially
In the state that height takes off lithium, positive electrode surface is easy and side reaction occurs for electrolyte, generates electrochemicaUy inert layer, and adjoint
The generation of Spinel and the equal impurity phase of rock salt, it is suppressed that the diffusion of lithium ion, at the same time along in bulk material
The loss of oxygen, reduces security performance；In addition, during removal lithium embedded, it is micro- inside second particle caused by changing due to multiphase
The generation of crackle causes electrolyte to be further exacerbated by the corrosion of material, and surface impedance further increases.These question synthesis are led
The safety problem hidden danger for drastically declining and becoming more and more important of chemical property is caused.
The method for promoting nickelic tertiary cathode material chemical property at present mainly has surface cladding and element doping.Patent
CN 107331852A propose a kind of using oxide (Nb2O5, ZrO2And Y2O3) surface coated side is carried out to tertiary cathode material
Method, coating reduce the side reaction of electrolyte and positive electrode to a certain extent, and cycle performance and the heat for improving material are steady
It is qualitative, but effect is limited, while counter productive can be brought, because the metal oxide of cladding is inert material, it is suppressed that lithium
The transmission of ion and electronics.Shao-Kang Hu et al. (Journal of Power Sources, 188, (2009) 564-569)
By by Zr (OC3H7)4And LiNi1/3Co1/3Mn1/3O2Wet-mixing stirring is carried out in propyl alcohol, and is evaporated at 80-90 DEG C,
It is then roasted 5 hours at 450 DEG C and obtains ZrO2Surface coated LiNi1/3Co1/3Mn1/3O2Positive electrode, ZrO2Surface packet
Coating reduces the side reaction of bulk material and electrolyte to a certain extent, it is suppressed that and capacity attenuation improves cycle performance,
But also inevitably lead to the decline of first discharge specific capacity and high rate performance.107240690 A of patent CN use wet method
Mixed method, by nano silicon dioxide or zirconia-coated in ternary material surface, although cycle performance is improved,
But a degree of reduction is also presented in first discharge specific capacity, in addition, its wet process used is unable to fully avoid handling
Influence of the process to bulk material structure, and process is complicated, it is difficult to realize industrialization.104995769 A of patent CN are by mixing
Miscellaneous oxide dry method coats stratified material, and cycle performance is improved, but its clad is to the contribution function list of material property
One, and its method is coated on finished product, is heat-treated using high temperature post, and the stratiform material of surface doping is hardly formed
Material, only forms certain thickness clad, there is the inhibition spread to lithium ion.105938901 A of patent CN pass through
Oxide dry method coats stratified material, and cycle performance, which has, to be improved, but its covering amount is smaller, and without carrying out the suitable later stage
Heat treatment, it is difficult to be uniformly wrapped on material to lead to clad, and the solid solid interface between clad and bulk material does not connect,
The diffusion of lithium ion is hindered, and hinders the diffusion of electrolyte.
Invention content
In view of problem above existing for this field, the present invention provides a kind of surfaces to be modified nickelic tertiary cathode material, carries
High nickelic tertiary cathode material discharge capacity for the first time, coulombic efficiency, and improve the cyclical stability and multiplying power of material
Performance.
The present invention also provides the preparation method that a kind of nano-oxide surface is modified nickelic tertiary cathode material, the preparation sides
Method includes dry method cladding process and high-temperature post-treatment technique, and the surface that the former is suitable for industrialized production is modified, and the latter contributes to
Improve the lithium ion conductivity of solid solid interface, it is expected that this cladding process can be in batches at production modification in industrial large-scale production
The performance of nickelic tertiary cathode material.
A further object of the present invention is to propose that the surface is modified lithium ion battery made of nickelic tertiary cathode material.
Realize that above-mentioned purpose technical solution of the present invention is：
A kind of nickelic tertiary cathode material of surface modification is that clad surface is modified on nickelic tertiary cathode material kernel
Layer；
The nickelic tertiary cathode material kernel is Li1+kNixCoyMzO2, wherein M is one in Al, Mn, Ti, Mg
Kind, -0.1≤k≤0.1,0 < x <, 1,0 < y <, 1,0 < z < 1.
The surface reforming layer is formed by two kinds of surface modifying species, and one of which is yttria-stabilized zirconia
(YSZ), another is selected from metal oxide MeOx, metal fluoride MeFx, metal phosphate Me (PO4)xOr in C extremely
Few one kind, wherein Me are one kind in Mn, Ti, Co, Cr, V, Fe, Nb, Mo, W and Y.
This surface modifying species has from the surface of nickelic tertiary cathode material particle closer to inside, dense in what is more declined
Spend gradient.
Lacking oxygen is formed by adding yttrium oxide into zirconium oxide in YSZ materials in the present invention, so as to by Y3+Carry out generation
For Zr4+A part in ion.As a result, by three O2-Ion replaces four O2-Ion can finally form Lacking oxygen
(oxygen vacancy).The space caused by the Lacking oxygen that generates in this way, forms very on the surface of positive active material
The space of lithium ion deintercalation can mostly be made.If there are the paths of Lacking oxygen to be connected as a result, lithium ion conduction degree can will very
Height is based on this Lacking oxygen, if the positive active material comprising the YSZ as surface-modified particles is suitable for secondary cell,
Capacitance loss can then be minimized.Another surface-modified particles is metal oxide MeOx, metal fluoride MeFx, metal
Phosphate Me (PO4)xOr at least one of C, wherein Me are Mn, Ti, Co, Cr, V, Fe, Nb, Mo, W and Y.It can press down
The side reaction of prepared material and electrolyte, is coated on material surface, can resist the corrosion of trace HF in electrolyte, and protection is high
The integrality of nickel ternary material.Secondly, by dry method cladding and Post isothermal treatment process, complete surface coating layer is formed, is pressed down
The formation of the micro-crack of material is made.In addition, being coated jointly by YSZ and another surface-modified particles, achieves and expect not
The synergistic effect arrived greatly improves the chemical property of material.
It is the preferred technical solution of the present invention below.
Wherein, the grain size that the surface is modified nickelic tertiary cathode material is 0.1~20 μm, the surface modifying species
Granular size be 10~100nm.
Wherein, in the surface reforming layer, yttria-stabilized zirconia (YSZ) chemical formula is Zr(1-a)YaO2-a/2, wherein
0.01 a≤0.3 <, the quality of yttria-stabilized zirconia are 0.1~5% of nuclear mass in nickelic tertiary cathode material, in addition
A kind of quality of surface modifying species is 0.1~5% of nuclear mass in nickelic tertiary cathode material.
It is preferred for the Lacking oxygen that the yttria-stabilized zirconia (YSZ) of this modified material is included, relative to nickelic three
The total amount of first positive electrode, range of the Lacking oxygen amount in 0.01-5000ppm.
The surface is modified the preparation method of nickelic tertiary cathode material, is at least one of following methods：
First method is that nickelic tertiary cathode material and surface modifying species are carried out solid phase mixing cladding, will be coated
Intermediate product afterwards is heat-treated, and the nickelic tertiary cathode material of surface modification is obtained.
Second method is to carry out at least one of the presoma of nickelic tertiary cathode material, surface-modified particles
Solid phase mixing coat, then with monohydrate lithium hydroxide (LiOHH2O it) is mixed, then carries out two sections of high-temperature heat treatments, obtained
The nickelic tertiary cathode material that surface is modified；
The third method is, by a kind of carry out solid phase in the presoma of nickelic tertiary cathode material, surface-modified particles
Mixing cladding, carries out two sections of high-temperature heat treatments, obtains intermediate product after then being mixed with monohydrate lithium hydroxide, will be in gained
Between another in product and surface-modified particles carry out solid phase mixing cladding, then carry out third section heat treatment, obtain to surface and change
The nickelic tertiary cathode material of property.
Wherein, the equipment that the solid phase mixing cladding uses is mechanical fusion machine, roller mill (roll-mill), ball mill
(ball-mill), in high-energy ball mill (high energy ball mill), planetary mill (planetary mill)
At least one.
Wherein, the heat treatment, the heat treatment of two sections of high-temperature heat treatments, first segment, second segment heat treatment are in oxygen gas
It is carried out under atmosphere.
Preferably, in the first method, the temperature of heat treatment is 300~700 DEG C, time of heat treatment is 1~
10h。
Wherein, in the second method, the condition of two sections of high-temperature heat treatments is：It is heat-treated 3 at a temperature of 400~800 DEG C
~10h, and, 10~30h is heat-treated at a temperature of 650~900 DEG C.
Wherein, in the third described method, the condition of two sections of high-temperature heat treatments is：It is heat-treated at a temperature of 400~800 DEG C
3~10h, and, 10~30h is heat-treated at a temperature of 650~900 DEG C, the temperature of third section heat treatment is 400~800 DEG C, the time
For 3~10h.
It is modified lithium ion battery made of nickelic tertiary cathode material with the surface.
Compared with prior art, the present invention has the following advantages：
(1) the nickelic tertiary cathode material of surface modification provided by the invention, surface modifying species (including oxide, fluorination
Object, phosphate, C etc.) it is coated on bulk material surface, reduce the side reaction of nickelic tertiary cathode material and electrolyte, inhibits
The irreversible capacity loss of material, improves cycle performance.The surface of the application is modified nickelic tertiary cathode material embodiment 2
100 weeks circulation volume conservation rates be 85.5%, and 100 weeks circulation volume conservation rates of comparative example are only 76.4%.
(2) YSZ materials with Lacking oxygen and other surfaces modified material (including oxide, the fluorine provided in the present invention
Compound, phosphate, C etc.) a kind of unexpected synergistic effect of common cladding generation, greatly improve the electrochemistry of material
Energy.YSZ is a kind of oxide containing Lacking oxygen, is conducive to lithium ion mobility, the nickelic tertiary cathode being modified by its surface
Material, surface have faster lithium ion mobility rate, and being covered in the surface of nickelic tertiary cathode material can improve well
Lithium ion diffusion problem improves the high rate performance of material.
(3) the present invention provides a kind of surface modification technology suitable for industrialized production, which coats comprising dry method
Technique and high-temperature post-treatment technique, the surface that the former is suitable for industrialized production are modified, and the latter helps to improve solid solid interface
Lithium ion conductivity, it is expected that this cladding process can be in batches at the modified nickelic tertiary cathode material of production in industrial large-scale production
The performance of material.
Description of the drawings
Fig. 1 is modified the SEM photograph of nickelic tertiary cathode material for 2 control surfaces of embodiment.
Fig. 2 is that surface prepared by embodiment 2 is modified nickelic tertiary cathode material and the first charge-discharge curve of comparative example.
Fig. 3 is that surface prepared by embodiment 2 is modified nickelic tertiary cathode material and the high rate performance figure of comparative example.
Fig. 4 is the cycle performance figure that surface prepared by embodiment 2 is modified nickelic tertiary cathode material and comparative example.
Specific implementation mode
Illustrate the present invention below by most preferred embodiment.Those skilled in the art institute it should be understood that, embodiment is only used for
It illustrates rather than for limiting the scope of the invention.
In used material, nano-oxide YSZ (Zr0.92Y0.08O1.96) it is purchased in market, by grinding to obtain average grain diameter
The YSZ of 50nm, range of the Lacking oxygen amount in 0.01-5000ppm.
Unless otherwise instructed, material is purchased in market in embodiment.Unless otherwise instructed, means used are this field routine
Means.
Embodiment 1
The positive electrode of the present embodiment is the nickelic tertiary cathode material (molecular formula for being 13 μm in average grain diameter：
LiNi0.88Co0.09Al0.03O2) core surface formed 0.5% (mass fraction) average grain diameter be 50nm nano-oxide YSZ
(Zr0.92Y0.08O1.96) and 0.5% (mass fraction) 50nm nano-oxide aluminium oxide (MnO2) surface reforming layer.
Preparation method is as follows：
Weigh the nickelic tertiary cathode material (LiNi of 300.0g0.88Co0.09Al0.03O2), 1.500g nano-oxides YSZ
(Zr0.92Y0.08O1.96), 1.500g nano-oxide manganese dioxide (MnO2), using mechanical fusion machine.It is equal to mix 5min claddings
It is even, the nickelic tertiary cathode material of surface modification is then can be obtained after 600 DEG C of heat treatment 4h in oxygen atmosphere.
Electrochemical property test is as follows：
According to mass ratio it is 8 by target product and conductive agent acetylene black, binder PVDF (Kynoar):1:1 mixing
Uniformly, it then is mixed into the slurry of certain viscosity with NMP (N- methyl-pyrrolidons), slurry is coated uniformly on Al foils,
80 DEG C, dry 4h is washed into the electrode slice of a diameter of 14mm, the dry 12h of 80 DEG C of vacuum is carried out after rolling.The electrode slice is transferred to
In glove box, as positive plate, then using metal lithium sheet as cathode, 2400 films of Celgard are diaphragm, 1mol L-1LiPF6/EC
+ DEC+DMC (volume ratios 1:1:1) it is electrolyte, in glove box (German M.Braun companies, O2And H2O mass fractions are respectively less than
2032 button cells are assembled in 0.1ppm), the battery assembled carries out charge-discharge test (China on CT2001 indigo plant electric testers
Wuhan Jin Nuo Co., Ltds), 25 DEG C ± 3 DEG C of temperature.
Electro-chemical test shows that initial charge, specific discharge capacity are respectively in 0.1C, 2.5-4.3V voltage range
237.9 with 210.3mAh g-1, first charge-discharge coulombic efficiency is 88.4%, (3C), 2.5-4.3V voltages under the conditions of high magnification
Specific discharge capacity in range is 174.5mAh g-1, 100 circulation volume conservation rates are under the conditions of 1.0C, 2.5-4.3V
85.3%.
Embodiment 2
The positive electrode of the present embodiment is the nickelic tertiary cathode material (molecular formula for being 13 μm in average grain diameter：
LiNi0.88Co0.09Al0.03O2) core surface formed 1% (mass fraction) average grain diameter be 50nm nano-oxide YSZ
(Zr0.82Y0.18O1.91) and 0.5% (mass fraction) 50nm nano-oxide manganese dioxide (MnO2) surface reforming layer.
Preparation method is as follows：
Weigh the nickelic tertiary cathode material (LiNi of 300.0g0.88Co0.09Al0.03O2), 3.000g nano-oxides YSZ
(Zr0.92Y0.08O1.96), 1.500g nano-oxide manganese dioxide (MnO2), it is evenly coated using mechanofusion method, then in oxygen
The nickelic tertiary cathode material of surface modification is can be obtained during atmosphere is enclosed after 600 DEG C of heat treatment 4h.The stereoscan photograph of material
See Fig. 1.
Electrochemical property test is the same as embodiment 1；
Electro-chemical test shows that initial charge, specific discharge capacity are respectively in 0.1C, 2.5-4.3V voltage range
232.1 with 211.9mAh g-1, first charge-discharge coulombic efficiency is 91.3%, as shown in Figure 2；Under the conditions of high magnification (3C),
Specific discharge capacity in 2.5-4.3V voltage ranges is 174.2mAh g-1, as shown in Figure 3；Under the conditions of 1.0C, 2.5-4.3V
100 circulation volume conservation rates are 87.2%, as shown in Figure 4.
Embodiment 3
The positive electrode of the present embodiment is the nickelic tertiary cathode material (molecular formula for being 13 μm in average grain diameter：
LiNi0.88Co0.09Al0.03O2) core surface formed 1% (mass fraction) average grain diameter be 50nm nano-oxide YSZ
(Zr0.92Y0.08O1.96) and 0.5% (mass fraction) manganese phosphate (Mn3(PO4)2) surface reforming layer.
Preparation method is as follows：
Weigh the nickelic tertiary cathode material (LiNi of 300.0g0.88Co0.09Al0.03O2), 3.000g nano-oxides YSZ
(Zr0.92Y0.08O1.96), 1.500g manganese phosphates (Mn3(PO4)2), it is evenly coated using mechanofusion method, then in oxygen atmosphere
It can be obtained the nickelic tertiary cathode material of surface modification after 600 DEG C of heat treatment 4h.
Electrochemical property test is the same as embodiment 1；
Electro-chemical test shows that initial charge, specific discharge capacity are respectively in 0.1C, 2.5-4.3V voltage range
234.3 with 210.9mAh g-1, first charge-discharge coulombic efficiency is 90.0%, (3C), 2.5-4.3V voltages under the conditions of high magnification
Specific discharge capacity in range is 172mAh g-1, 100 circulation volume conservation rates are under the conditions of 1.0C, 2.5-4.3V
88.2%.
Embodiment 4
The positive electrode of the present embodiment is, in nickelic ternary anode material precursor (molecular formula：Ni0.88Co0.09Al0.03
(OH)2) core surface formed 0.5% (mass fraction) manganous fluoride (MnF2) and 1% (mass fraction) 50nm nano-oxide
The surface reforming layer of YSZ (Zr0.92Y0.08O1.96).
Preparation method is as follows：
Weigh the nickelic ternary anode material precursor (molecular formula of 300.0g：Ni0.88Co0.09Al0.03(OH)2), 1.500g fluorine
Change manganese (MnF2), the nano-oxide YSZ (Zr of 3.000g0.92Y0.08O1.96), the monohydrate lithium hydroxide (LiOH of 141.140g
H2O), it is evenly coated using mechanofusion method mixing, obtains Preburning material.Then 480 DEG C of heat treatment 4h are subsequent in oxygen atmosphere
After being warming up to 740 DEG C of 20 hours of heat treatment, the nickelic tertiary cathode material of surface modification is obtained.
Electrochemical property test is the same as embodiment 1；
Electro-chemical test shows that initial charge, specific discharge capacity are respectively in 0.1C, 2.5-4.3V voltage range
229.0 with 208.3mAh g-1, first charge-discharge coulombic efficiency is 90.96%, (3C), 2.5-4.3V electricity under the conditions of high magnification
It is 172.7mAh g to press the specific discharge capacity in range-1, 100 circulation volume conservation rates are under the conditions of 1.0C, 2.5-4.3V
85.9%.
Embodiment 5
The positive electrode of the present embodiment is, in nickelic ternary anode material precursor (molecular formula：Ni0.88Co0.09Al0.03
(OH)2) core surface formed 0.5% (mass fraction) average grain diameter be 50nm nano-manganese dioxide (MnO2) clad after,
With the baking mixed rear obtained intermediate products of lithium hydroxide, the nano oxidized of the 50nm of one layer 1% (mass fraction) is then coated again
Object YSZ (Zr0.92Y0.08O1.96) surface reforming layer.
Preparation method is as follows：
Weigh the nickelic ternary anode material precursor (molecular formula of 300.0g：Ni0.88Co0.09Al0.03(OH)2), 1.500g bis-
Manganese oxide (MnO2), the monohydrate lithium hydroxide (LiOHH of 141.140g2O), it is evenly coated, is obtained using mechanofusion method mixing
Preburning material.Then 480 DEG C of heat treatment 4h obtain centre after being then warming up to 740 DEG C of 20 hours of heat treatment in oxygen atmosphere
Product.Finally, the intermediate product of 30.000g and the nano-oxide YSZ (Zr of 0.300g are weighed again0.92Y0.08O1.96), it uses
Mechanofusion method is evenly coated, and then can be obtained the nickelic ternary of surface modification after 600 DEG C of heat treatment 4h in oxygen atmosphere
Positive electrode.
Electrochemical property test is the same as embodiment 1；
Electro-chemical test shows that initial charge, specific discharge capacity are respectively in 0.1C, 2.5-4.3V voltage range
229.6 with 208.1mAh g-1, first charge-discharge coulombic efficiency is 90.63%, (3C), 2.5-4.3V electricity under the conditions of high magnification
It is 171.4mAh g to press the specific discharge capacity in range-1, 100 circulation volume conservation rates are under the conditions of 1.0C, 2.5-4.3V
85.1%.
Embodiment 6
The positive electrode of the present embodiment is, in nickelic ternary anode material precursor (molecular formula：Ni0.88Co0.09Al0.03
(OH)2) core surface formed 0.5% (mass fraction) average grain diameter be 50nm nano-oxide titanium dioxide (TiO2) packet
After coating, with the baking mixed rear obtained intermediate products of lithium hydroxide, then coat the 50nm's of one layer 1% (mass fraction) again
Nano-oxide YSZ (Zr0.92Y0.08O1.96) surface reforming layer.
Preparation method is as follows：
Weigh the nickelic ternary anode material precursor (molecular formula of 300.0g：Ni0.88Co0.09Al0.03(OH)2), 1.500g receives
Rice oxide titanium dioxide (TiO2), the monohydrate lithium hydroxide (LiOHH of 141.140g2O), mixed and wrapped using mechanofusion method
It covers uniformly, obtains Preburning material.Then 480 DEG C of heat treatment 4h are then warming up to 740 DEG C of 20 hours of heat treatment in oxygen atmosphere
Afterwards, intermediate product is obtained.Finally, the intermediate product of 30.000g and the nano-oxide YSZ of 0.300g are weighed again
(Zr0.92Y0.08O1.96), it is evenly coated using mechanofusion method, then be can be obtained after 600 DEG C of heat treatment 4h in oxygen atmosphere
The nickelic tertiary cathode material that surface is modified.
Electrochemical property test is the same as embodiment 1；
Electro-chemical test shows that initial charge, specific discharge capacity are respectively in 0.1C, 2.5-4.3V voltage range
236.6 with 210.1mAh g-1, first charge-discharge coulombic efficiency is 88.8%, (3C), 2.5-4.3V voltages under the conditions of high magnification
Specific discharge capacity in range is 171mAh g-1, 100 circulation volume conservation rates are 84% under the conditions of 1.0C, 2.5-4.3V.
Comparative example
As a comparison, the nickelic tertiary cathode material (LiNi being modified without surface0.88Co0.09Al0.03O2), it fills for the first time
Specific discharge capacity is respectively：235.8 with 210.6mAh g-1, first charge-discharge efficiency 89.3%；In 1.0C, 2.5-4.3V item
Capacity retention ratio is 76.4% after lower 100 cycles of part.Charge and discharge test result is shown in Fig. 2-4 (bare-NCA is denoted as in figure).
Nickelic tertiary cathode material prepared by the nickelic tertiary cathode material and comparative example that surface prepared by embodiment 1-2 is modified
Material, the amount and material surface total alkali content test result and assembling lithium ion battery of surface modifying species and surface modifying species
First charge-discharge efficiency and as shown in the table in the cycle performance data of 2.5-4.3V.
1 embodiment and comparative example electrochemical property test tables of data of table
This surface-modified particles is coated on the outer surface of the nickelic tertiary cathode material particle and forms clad.It is logical
Later phase heat treatment process has transition zone, improves solid solid interface between the surface reforming layer and body phase material particle
Lithium ion conductivity.The surface of the application is modified nickelic tertiary cathode material embodiment 2 compared with comparative example, and will discharge ratio for the first time
Capacity is by 210.6mAh g-1It is increased to 211.9mAh g-1, specific discharge capacity is by 168.3mAh g when 3C-1It is increased to 174.2mAh
g-1。
Above embodiment be only the preferred embodiment of the present invention is described, not to the scope of the present invention into
Row limits, under the premise of not departing from design spirit of the present invention, technical side of this field ordinary engineering and technical personnel to the present invention
The all variations and modifications that case is made should all be fallen into the protection domain of claims of the present invention determination.
Claims (10)
1. a kind of surface is modified nickelic tertiary cathode material, which is characterized in that coated on nickelic tertiary cathode material kernel
Surface reforming layer；
The nickelic tertiary cathode material kernel is Li1+kNixCoyMzO2, wherein M be Al, Mn, Ti, Mg in one kind, -0.1
1,0 < y < of≤k≤0.1,0 < x <, 1,0 < z < 1；
The surface reforming layer is formed by two kinds of surface modifying species, and one of which is yttria-stabilized zirconia, and in addition one
Kind is selected from metal oxide MeOx, metal fluoride MeFx, metal phosphate Me (PO4)xOr at least one of C, wherein Me
For one kind in Mn, Ti, Co, Cr, V, Fe, Nb, Mo, W and Y.
2. surface according to claim 1 is modified nickelic tertiary cathode material, which is characterized in that the surface is modified nickelic
The grain size of tertiary cathode material is 0.1~20 μm, and the granular size of the surface modifying species is 10~100nm.
3. surface according to claim 1 is modified nickelic tertiary cathode material, which is characterized in that the surface reforming layer
In, yttria-stabilized zirconia chemical formula is Zr(1-a)YaO2-a/2, wherein 0.01 a≤0.3 <, the matter of yttria-stabilized zirconia
Amount is 0.1~5% of nuclear mass in nickelic tertiary cathode material, the quality of another surface modifying species be nickelic ternary just
The 0.1~5% of pole material core quality.
4. claims 1 to 3 any one of them surface is modified the preparation method of nickelic tertiary cathode material, which is characterized in that
For at least one of following methods：
First method is nickelic tertiary cathode material and surface modifying species to be carried out solid phase mixing cladding, after cladding
Intermediate product is heat-treated, and the nickelic tertiary cathode material of surface modification is obtained.
Second method is that at least one of the presoma of nickelic tertiary cathode material, surface-modified particles are carried out solid phase
Mixing cladding, is then mixed with monohydrate lithium hydroxide, then carry out two sections of high-temperature heat treatments, and nickelic the three of surface modification are obtained
First positive electrode；
The third method is, by a kind of carry out solid phase mixing in the presoma of nickelic tertiary cathode material, surface-modified particles
Cladding carries out two sections of high-temperature heat treatments, obtains intermediate product after then being mixed with monohydrate lithium hydroxide, will be produced among gained
Object and another progress solid phase mixing cladding in surface-modified particles, then third section heat treatment is carried out, obtain surface modification
Nickelic tertiary cathode material.
5. preparation method according to claim 4, which is characterized in that the equipment that the solid phase mixing cladding uses is machinery
At least one of fusion machine, roller mill, ball mill, high-energy ball mill, planetary mill.
6. preparation method according to claim 4, which is characterized in that the heat treatment, two sections of high-temperature heat treatments, third section
Heat treatment is carried out under oxygen atmosphere.
7. preparation method according to any one of claim 4 to 6, which is characterized in that in the first method, heat treatment
Temperature be 300~700 DEG C, time of heat treatment is 1~10h.
8. preparation method according to any one of claim 4 to 6, which is characterized in that in the second method, two sections of height
Warming the condition handled is：3~10h is heat-treated at a temperature of 400~800 DEG C, and, it is heat-treated 10 at a temperature of 650~900 DEG C
~30h.
9. preparation method according to any one of claim 4 to 6, which is characterized in that in the third described method, two sections of height
Warming the condition handled is：3~10h is heat-treated at a temperature of 400~800 DEG C, and, it is heat-treated 10 at a temperature of 650~900 DEG C
The temperature of~30h, the heat treatment of third section are 400~800 DEG C, and the time is 3~10h.
10. being modified lithium ion battery made of nickelic tertiary cathode material with claims 1 to 3 any one of them surface.
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